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The Polarizable Charge Equilibration Model for Transition-Metal Elements

Kwon, Soonho and Naserifar, Saber and Lee, Hyuck Mo and Goddard, William A., III (2018) The Polarizable Charge Equilibration Model for Transition-Metal Elements. Journal of Physical Chemistry A, 122 (48). pp. 9350-9358. ISSN 1089-5639.

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The polarizable charge equilibration (PQEq) method was developed to provide a simple but accurate description of the electrostatic interactions and polarization effects in materials. Previously, we optimized four parameters per element for the main group elements. Here, we extend this optimization to the 24 d-block transition-metal (TM) elements, columns 4–11 of the periodic table including Ti–Cu, Zr–Ag, and Hf–Au. We validate the PQEq description for these elements by comparing to interaction energies computed by quantum mechanics (QM). Because many materials applications involving TM are for oxides and other compounds that formally oxidize the metal, we consider a variety of oxidation states in 24 different molecular clusters. In each case, we compare interaction energies and induced fields from QM and PQEq along various directions. We find that the original χ and J parameters (electronegativity and hardness) related to the ionization of the atom remain valid; however, we find that the atomic radius parameter needs to be close to the experimental ionic radii of the transition metals. This leads to a much higher spring constant to describe the atomic polarizability. We find that these optimized parameters for PQEq provide accurate interaction energies compared to QM with charge distributions that depend in a reasonable way on the coordination number and oxidation states of the transition metals. We expect that this description of the electrostatic interactions for TM will be useful in molecular dynamics simulations of inorganic and organometallic materials.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Naserifar, Saber0000-0002-1069-9789
Lee, Hyuck Mo0000-0003-4556-6692
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2018 American Chemical Society. Received: July 28, 2018; Revised: November 8, 2018; Published: November 9, 2018. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2017R1E1A1A03071049). This work was supported as part of the Computational Materials Sciences Program funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award Number DE-SC00014607. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant ACI-1548562. The authors declare no competing financial interest.
Funding AgencyGrant Number
National Research Foundation of Korea2017R1E1A1A03071049
Department of Energy (DOE)DE-SC00014607
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Issue or Number:48
Record Number:CaltechAUTHORS:20181112-081038938
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Official Citation:Polarizable Charge Equilibration Model for Transition-Metal Elements. Soonho Kwon, Saber Naserifar, Hyuck Mo Lee, and William A. Goddard, III. The Journal of Physical Chemistry A 2018 122 (48), 9350-9358 DOI: 10.1021/acs.jpca.8b07290
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90827
Deposited By: Tony Diaz
Deposited On:13 Nov 2018 17:31
Last Modified:26 Oct 2019 02:09

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